5-[(3,4-dibutylthien-2-yl)ethynyl]-5'-(triethylsilyl)ethynyl-2,2'-bipyridine | 794529-21-8

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡啶及其衍生物
• 英文名称: 5-[(3,4-dibutylthien-2-yl)ethynyl]-5'-(triethylsilyl)ethynyl-2,2'-bipyridine
• 英文别名: 2-[6-[5-[2-(3,4-Dibutylthiophen-2-yl)ethynyl]pyridin-2-yl]pyridin-3-yl]ethynyl-triethylsilane
• CAS: 794529-21-8
• 化学式: C₃₂H₄₀N₂SSi
• 分子量: 512.834
• InChiKey: NEQSEXJEKAHOOV-UHFFFAOYSA-N

物化性质

• 沸点：
  603.7±55.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  8.69
• 重原子数：
  36
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  54
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  5-[(3,4-dibutylthien-2-yl)ethynyl]-5'-(triethylsilyl)ethynyl-2,2'-bipyridine 在 四(三苯基膦)钯 N-碘代丁二酰亚胺 、 三乙胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 、 苯 为溶剂， 生成 5,5'-bis[(3,4-dibutyl-5-{[5'-(triethylsilylethynyl)-2,2'-bipyridin-5-yl]ethynyl}thien-2-yl)ethynyl]-2,2'-bipyridine
  参考文献：
  名称：

  Oligomeric Ligands Incorporating Multiple 5,5‘-Diethynyl-2,2‘-bipyridine Moieties Bridged and End-Capped by 3,4-Dibutylthiophene Units

  摘要：

  In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)(2)C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to hipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and endcapped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.

  DOI：

  10.1021/jo048435i
• 作为产物：
  描述：

  三乙基矽乙炔 在 bis-triphenylphosphine-palladium(II) chloride 、 copper(l) iodide 、 Pd(PPh3) sodium hydroxide 、 三乙胺 、 二异丙胺 作用下， 以 四氢呋喃 、 甲苯 、 苯 为溶剂， 反应 9.0h， 生成 5-[(3,4-dibutylthien-2-yl)ethynyl]-5'-(triethylsilyl)ethynyl-2,2'-bipyridine
  参考文献：
  名称：

  Oligomeric Ligands Incorporating Multiple 5,5‘-Diethynyl-2,2‘-bipyridine Moieties Bridged and End-Capped by 3,4-Dibutylthiophene Units

  摘要：

  In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)(2)C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to hipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and endcapped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.

  DOI：

  10.1021/jo048435i

文献信息

• Photophysical Properties of Ruthenium(II) Tris(2,2‘-bipyridine) Complexes Bearing Conjugated Thiophene Appendages
  作者：Anthony Harriman、Guillaume Izzet、Sébastien Goeb、Antoinette De Nicola、Raymond Ziessel

  DOI：10.1021/ic060921w

  日期：2006.11.1

  A small series of ruthenium(II) tris(2,2'-bipyridine) complexes has been synthesized in which ethynylated thiophene residues are attached to one of the 2,2'-bipyridine ligands. The photophysical properties depend on the conjugation length of the thiophene-based ligand, and in each case, dual emission is observed. The two emitting states reside in thermal equilibrium at ambient temperature and can be

  合成了少量的钌（II）三（2,2'-联吡啶）配合物，其中乙炔基噻吩残基连接到2,2'-联吡啶配体之一。光物理性质取决于基于噻吩的配体的缀合长度，并且在每种情况下均观察到双重发射。这两个发射态在环境温度下处于热平衡状态，可以通过发射光谱曲线拟合例程来解决。这允许在液体丁腈溶液和透明KBr圆盘中评估两种状态的性质。结论是，两种发射态均具有金属到配体的电荷转移（MLCT）特性，尽管存在共轭噻吩残基，但没有迹象表明pi低，π*-三重态，促进激发态歧管的非辐射衰减。这些系统的关键特征是，基于噻吩的配体施加的共轭长度有助于控制两个MLCT三重态的辐射衰减和非辐射衰减的速率常数。
• Oligomeric Ligands Incorporating Multiple 5,5‘-Diethynyl-2,2‘-bipyridine Moieties Bridged and End-Capped by 3,4-Dibutylthiophene Units
  作者：Sébastien Goeb、Antoinette De Nicola、Raymond Ziessel

  DOI：10.1021/jo048435i

  日期：2005.3.1

  In this work, we detail the synthesis and photophysical properties of a series of soluble polybipyridine ligands comprising one to five bipyridine units sandwiched between rigid carbon-carbon triple bonds substituted by 3,4-dibutylthiophene repeating units. The dual Sonogashira coupling reaction of 5,5'-dibromo-2,2'-bipyridine with TMS- and (CH3)(2)C(OH)-protected acetylene allows the synthesis of a dissymmetrically functionalized building block which was selectively deprotected at either the TMS or 2-hydroxyprop-2-yl site. Various combinations allow the interconnection of the terminal alkyne to 3,4-dibutyl-2,5-diiodothiophene or 3,4-dibutyl-2-iodothiophene leading to hipyridine frameworks bearing two acetylene-protected groups or one acetylenethiophene/one acetylene-protected function. It is possible therefore to construct dimeric to pentameric bipyridine ligands where the chelating subunit is bridged by a 3,4-dibutyl-2,5-diethynylthiophene spacer and endcapped by a 3,4-dibutyl-2-ethynylthiophene stopper. All cross-coupling reactions are promoted with palladium(0) tetrakistriphenylphosphine under mild conditions. Spectroscopic data for the new oligomers are discussed in terms of the extent of pi-electron conjugation. Upon increasing the number of pi-electrons from 24 to 104, there is a progressive lowering in the energy of absorption and fluorescence transitions, while the emission quantum yields remain essentially constant. The LUMO levels of these large molecules, estimated by cyclic voltammetry, lie in the range -3.06 to -3.18 eV.